Electron beam cured silicone release materials

ABSTRACT

Methods of electron beam curing nonfunctional polysiloxanes blended with functional polysiloxanes are provided. The resulting release materials are also provided.

This application is continuation-in-part and claims the benefit of U.S. application Ser. No. 13/126,365 (filed Oct. 29, 2009), which claims the benefit of U.S. Provisional Application No. 61/109,211 (filed Oct. 29, 2008), and U.S. Provisional Application No. 61/109,213 (filed Oct. 29, 2008); the entireties of which are herein incorporated by reference.

FIELD

The present disclosure relates to silicone release materials and release liners incorporating such release materials. In particular, the present disclosure relates to electron beam cured polysiloxanes, including low molecular weight polysiloxane fluids. The present disclosure also relates to electron beam cured blends of nonfunctional polysiloxanes and functional polysiloxanes.

SUMMARY

Briefly, in one aspect, the present disclosure provides a method of making a silicone release layer. The methods include applying a composition comprising a polysiloxane material on a substrate and electron beam curing the composition to crosslink the polysiloxane material.

In some embodiments, the polysiloxane material consists essentially of one or more polysiloxane fluids having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes, e.g., between 1,000 centistokes and 100,000 centistokes. In some embodiments, the polysiloxane material comprises a poly dimethylsiloxane. In some embodiments, all polysiloxane materials in the composition are nonfunctional polysiloxanes. In some embodiments, each nonfunctional polysiloxane is a polysiloxane fluid having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes, e.g., between 1,000 centistokes and 100,000centistokes.

In some embodiments, the polysiloxane material comprises a silanol terminated polysiloxane fluid having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes, e.g., between 1,000 and 100,000 centistokes. In some embodiments, each polysiloxane material in the composition is independently selected from the group consisting of nonfunctional polysiloxanes, silanol terminated polysiloxanes, and alkoxy terminated polysiloxanes, and vinyl terminated polysiloxanes.

In some embodiments, the composition is substantially free of catalysts and initiators. In some embodiments, the composition comprises no greater than 5 wt. % solvent.

In another aspect, the present disclosure provides a release coated substrate made according to any of the various methods of the present disclosure. In some embodiments, the electron beam cured composition comprises a polysiloxane fluid having a kinematic viscosity at 25° C. of no greater than 50,000 centistokes, e.g., between 1,000 centistokes and 50,000 centistokes that has been crosslinked. In some embodiments, the composition consists essentially of one or more nonfunctional polysiloxane fluids, each having a kinematic viscosity at 25° C. of no greater than 50,000 centistokes, e.g., between 1,000 centistokes and 50,000 centistokes, wherein the polysiloxane fluids have been crosslinked. In some embodiments, the composition comprises a silanol terminated polysiloxane fluid having a kinematic viscosity at 25° C. of no greater than 50,000 centistokes, e.g., between 1,000 centistokes and 50,000 centistokes that has been crosslinked. In some embodiments, the composition is substantially free of catalysts and initiators.

The above summary of the present disclosure is not intended to describe each embodiment of the present invention. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an exemplary release liner according to some embodiments of the present disclosure.

DETAILED DESCRIPTION

Pressure sensitive adhesives (PSAs) are an important class of materials. Generally, PSAs adhere to a substrate with light pressure (e.g., finger pressure) and typically do not require any post-curing (e.g., heat or radiation) to achieve their maximum bond strength. A wide variety of PSA chemistries are available including, e.g., acrylic, rubber, and silicone based systems.

Adhesives, including PSAs are often used as free films or as supported films, e.g., single- and double-coated tapes. Often, release liners are used to protect the adhesive layer during handling (e.g., processing, shipping, storing, and converting) and use (e.g., application to a substrate). Release liners typically comprise a substrate coated with a release material. In use, the release liner is removed from the adhesive layer, exposing the adhesive layer so that it may adhered to the desired target substrate. In such applications, the release liner may be reused, but is frequently discarded. In some applications, an adhesive article may be self-wound. In such cases, a substrate is coated on one side with a release material, with the adhesive bonded to the opposite side of the substrate. When the article is wound upon itself (i.e., self wound), the exposed adhesive surface comes in contact with the release coated side of the substrate. In use, the roll is unwound, and the adhesive is applied to the desired target substrate.

Crosslinked silicones have been used as release materials. Conventional silicone release materials are cured by thermal processes using specific types of catalysts. For example, platinum catalysts have been used with addition cure systems, peroxides (e.g., benzoyl peroxide) have been used with hydrogen-abstraction cure systems, and tin catalysts have been used with moisture/condensation cure systems.

Generally, these approaches require reactive functional groups attached to the siloxane backbone. For example, addition-cure, platinum-catalyzed systems generally rely on a hydrosilation reaction between silicon-bonded vinyl functional groups and silicon-bonded hydrogens. In general, it may be desirable to have a silicone release system that can be cured without the use of catalysts. It can also be useful to provide release coatings that do not require specific functional groups for proper curing.

UV-cured and electron-beam cured silicone release materials have been used. These systems require the use of catalysts and specific functional groups. In particular, acrylate-functional and epoxy-functional silicones have been radiation cured in the presence of catalysts.

The present inventors have discovered new methods for producing release layers, and release articles comprising such release layers. Generally, the methods include electron beam curing silicone materials to form a crosslinked polysiloxane network. Generally, the methods can be used with functional and non-functional silicone materials and blends thereof.

In contrast to previous methods for curing silicone materials, the methods of the present disclosure do not require the use of catalysts or initiators. Thus, the methods of the present disclosure can be used to cure compositions that are “substantially free” of such catalysts or initiators. As used herein, a composition is “substantially free of catalysts and initiators” if the composition does not include an “effective amount” of a catalyst or initiator. As is well understood, an “effective amount” of a catalyst or initiator depends on a variety of factors including the type of catalyst or initiator, the composition of the curable material, and the curing method (e.g., thermal cure, UV-cure, and the like). In some embodiments, a particular catalyst or initiator is not present at an “effective amount” if the amount of catalyst or initiator does not reduce the cure time of the composition by at least 10% relative to the cure time for the same composition at the same curing conditions, absent that catalyst or initiator.

Generally, the silicone materials useful in the present disclosure are polysiloxanes, i.e., materials comprising a polysiloxane backbone. In some embodiments, the nonfunctionalized silicone materials can be a linear material described by the following formula illustrating a siloxane backbone with aliphatic and/or aromatic substituents:

R1 through R4 represent the substituents pendant from the siloxane backbone. Each R5 may be independently selected and represent the terminal groups. Subscripts n and m are integers, and at least one of m or n is not zero.

In some embodiments, the silicone material is a nonfunctional polysiloxane material. As used herein, a “nonfunctionalized polysiloxane material” is one in which the R1, R2, R3, R4, and R5 groups are nonfunctional groups. As used herein, “nonfunctional groups” are either alkyl or aryl groups consisting of carbon, hydrogen, and in some embodiments, halogen (e.g., fluorine) atoms. In some embodiments R1, R2, R3, and R4 are independently selected from at least one of an alkyl group and an aryl group, each R5 is an alkyl group and n and m are integers, and at least one of m or n is not zero. In some embodiments, one or more of the alkyl or aryl groups may contain a halogen substituent, e.g., fluorine. For example, in some embodiments, one or more of the alkyl groups may be —CH₂CH₂C₄F₉.

In some embodiments, R5 is a methyl group, i.e., the nonfunctionalized polysiloxane material is terminated by trimethylsiloxy groups. In some embodiments, R1 and R2 are alkyl groups and n is zero, i.e., the material is a poly(dialkylsiloxane). In some embodiments, the alkyl group is a methyl group, i.e., poly(dimethylsiloxane) (“PDMS”). In some embodiments, R1 is an alkyl group, R2 is an aryl group, and n is zero, i.e., the material is a poly(alkylarylsiloxane). In some embodiments, R1 is a methyl group and R2 is a phenyl group, i.e., the material is poly(methylphenylsiloxane). In some embodiments, R1 and R2 are alkyl groups and R3 and R4 are aryl groups, i.e., the material is a poly(dialkyldiarylsiloxane). In some embodiments, R1 and R2 are methyl groups, and R3 and R4 are phenyl groups, i.e., the material is poly(dimethyldiphenylsiloxane).

In some embodiments, the polysiloxane backbone may be linear. In some embodiments, the functionalized polysiloxane materials may be branched. For example, one or more of the R1, R2, R3, and/or R4 groups may be a linear or branched siloxane with functional or nonfunctional (e.g., alkyl or aryl, including halogenated alkyl or aryl) pendant and terminal R5 groups.

In some embodiments, the polysiloxane backbone may be cyclic. For example, the silicone material may be octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, or dodecamethylcyclohexasiloxane.

In some embodiments, the polysiloxane material may be functional. Generally, functional silicone systems include specific reactive groups attached to the polysiloxane backbone of the starting material (for example, acrylic, vinyl, amine, hydroxyl and alkoxy groups). As used herein, a “functionalized polysiloxane material” is one in which at least one of the R-groups of Formula 2 is a functional group.

In some embodiments, a functional polysiloxane material is one in which at least 2 of the R-groups are functional groups. Generally, the R-groups of Formula 2 may be independently selected. In some embodiments, all functional groups are hydroxy groups and/or alkoxy groups. In some embodiments, the functional polysiloxane is a silanol terminated polysiloxane, e.g., a silanol terminated poly(dimethylsiloxane). In some embodiments, the functional silicone is an alkoxy terminated poly(dimethyl siloxane), e.g., trimethyl siloxy terminated poly(dimethyl siloxane). In some embodiments, the functional polysiloxane is a vinyl terminated polysiloxane. In some embodiments, the functional polysiloxane is an amine terminated polysiloxane. In some embodiments, the functional polysiloxane is an acrylate terminated polysiloxane.

Other functional groups include those having an unsaturated carbon-carbon bond such as alkene-containing groups (e.g., vinyl groups and allyl groups) and alkyne-containing groups.

In addition to functional R-groups, the R-groups may be nonfunctional groups, e.g., alkyl or aryl groups, including halogenated (e.g., fluorinated) alky and aryl groups. In some embodiments, the functionalized polysiloxane materials may be branched. For example, one or more of the R groups may be a linear or branched siloxane with functional and/or non-functional substituents. In some embodiments, the functionalized polysiloxane materials may be cyclic.

Generally, the silicone materials may be oils, fluids, gums, elastomers, or resins, e.g., friable solid resins. Generally, lower molecular weight, lower viscosity materials are referred to as fluids or oils, while higher molecular weight, higher viscosity materials are referred to as gums; however, there is no sharp distinction between these terms. Elastomers and resins have even higher molecular weights that gums, and typically do not flow. As used herein, the terms “fluid” and “oil” refer to materials having a dynamic viscosity at 25° C. of no greater than 1,000,000 mPa·sec (e.g., less than 600,000 mPa·sec), while materials having a dynamic viscosity at 25° C. of greater than 1,000,000 mPa·sec (e.g., at least 10,000,000 mPa·sec) are referred to as “gums”.

In order to obtain the low thicknesses generally desirable for release material, it is often necessary to dilute high molecular weight materials with solvents in order to coat or otherwise apply them to a substrate. In some embodiments, it may be preferable to use low molecular weight silicone oils or fluids, including those having a dynamic viscosity at 25° C. of no greater than 200,000 mPa·sec, no greater than 100,000 mPa·sec, or even no greater than 50,000 mPa·sec.

In some embodiments, it may be useful to use materials compatible with common solventless coating operations, including, e.g., those having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes (cSt), no greater than 50,000 cSt, e.g., no greater than 40,000 cSt, or even no greater than 20,000 cSt. In some embodiments, it may be desirable to use a combination of silicone materials, wherein at least one of the silicone materials has a kinematic viscosity at 25° C. of at least 1,000 centistokes (cSt), e.g., 5,000 cSt, at least 10,000 cSt, or even at least 15,000 cSt. In some embodiments, it may be desirable to use silicone materials having a kinematic viscosity at 25° C. of between 1000 cSt and 100,000 cSt, e.g., between 5,000 cSt and 100,000 cSt, or even between 10,000 cSt and 100,000 cSt. In some embodiments, it may be desirable to use silicone materials having a kinematic viscosity at 25° C. of between 1000 cSt and 50,000 cSt, e.g., between 5,000 cSt and 50,000 cSt, or even between 10,000 cSt and 50,000 cSt.

In some embodiments, blends of functional polysiloxanes and non-functional polysiloxanes include additives. For example, a cross-linking additive, such as a methyl hydride siloxane, is useful in some embodiments. Another exemplary additive is an anchoring additive, such as alkoxysilanes.

The amount of functional polysiloxane used in the presently disclosed blends varies according to many factors, such as the specific type of materials use, the finish use application, and the like. The presently disclosed blends of polysiloxanes and non-functional polysiloxanes include, in some embodiments, at least 10 wt % of at least one functional polysiloxanes based on the total weight of the blend. In some embodiments, the presently disclosed blends include at least 25 wt % of at least one functional polysiloxanes based on the total weight of the blend.

The amount of non-functional polysiloxane used in the presently disclosed blends varies according to many factors, such as the specific type of materials use, the finish use application, and the like. The presently disclosed blends polysiloxanes and non-functional polysiloxanes include, in some embodiments, at least 90 wt % of at least one non-functional polysiloxane based on the total weight of the blend. In some embodiments, the presently disclosed blends include at least 5 wt % of at least one functional polysiloxane based on the total weight of the blend.

EXAMPLE

A commercially available tape was used to evaluate the release and readhesion properties associated with the various electron beam cured release coating. The adhesive (ADH) was a crosslinked acrylic copolymer. ADH is available as a 51 micrometer (2 mil) thick transfer tape under the trade designation 467MP from 3M Company.

Non-functional Silicone Materials. Examples 1 through 4 were prepared by electron beam curing non-functional silicone materials. Coating materials were prepared by dissolving DC-200 silicone fluid (30,000 cSt, from Dow Chemical Company) in heptane to produce a 30 wt. % solids solution. This coating was applied with a flat stiff blade at 70 kPa (10 psi) pressure onto a polycoated kraft paper substrate (58# PCK from Jencoat). The samples were dried at room temperature. The resulting samples had a dry coat weight of 0.6 to 0.8 gram/square meter (0.14 to 0.20 grains per four inch by six inch sample).

The nonfunctional silicone material was electron beam cured according to the following procedure. The samples were cured using an acceleration voltage of 280 keV at various dosage levels.

E-Beam Curing Procedure. E-beam curing was performed on a Model CB-300 electron beam generating apparatus (available from Energy Sciences, Inc. (Wilmington, Mass.). Generally, a support film (e.g., polyester terephthalate support film) was run through the inerted chamber of the apparatus. Samples of uncured material were attached to the support film and conveyed at a fixed speed of about 6.1 meters/min (20 feet/min) through the inerted chamber and exposed to electron beam irradiation. For e-beam dosages of less than 18 Mrad, a single pass through the e-beam chamber was sufficient. To obtain higher dosages, e.g., 18 and 20 Mrad, two passes were required.

Adhesives applied to the cured release surface using both a “Dry Lamination” and “Wet-Cast” procedure. For the Dry Lamination samples, a 50 micron (2.0 mil) primed PET film (product 3SAB from Mitsubishi) was adhered to the transfer adhesive and pulled off to create the test samples. The adhesive side of the tape was then dry laminated onto the cured silicone coating of each sample using two passes of a 2 kg rubber roller. For the Wet Cast samples, the adhesives were cast directly on the cured silicone coatings of the examples and cured with ultraviolet radiation. A 50 micron (2.0 mil) primed PET film (product 3SAB from Mitsubishi) was then laminated to the cured adhesive to form the test samples.

Release Test Procedure. The PET-backed tape samples were peeled from the liner at an angle of 180° and at a rate of 230 cm/min (90 inches/minute). An IMass model SP2000 peel tester obtained from IMASS, Inc., Accord, Mass., was used to record the peel force.

Readhesion Test Procedure. To determine the readhesion value, the PET-backed tape samples were peeled from the liner using the Release Test method and the tape was then applied to the surface of a clean stainless steel panel. The tape sample was rolled down against the panel by means of two passes (forward and back) with a 2 kg rubber roller at 61 cm/min (24 inches/min). The readhesion value was a measure of the force required to pull the tape from the steel surface at an angle of 180° at a rate of 30.5 cm/min (12 inches/minute). The IMass model SP2000 peel tester was used to record the peel force.

The electron beam dose, liner release and readhesion for the dry-laminated samples are summarized in Table 1A. Similarly, the electron beam dose, liner release and readhesion for the wet-cast samples are summarized in Table 1B. The release and readhesion were measured initially and after a five day dwell of the adhesive against the release coating at 32° C. (90° F.) and 90% relative humidity (90/90).

TABLE 1A Release and readhesion results for dry laminated samples. Initial 90/90 (gm/2.54 cm) (gm/2.54 cm) Dose Re- Readhe- Re- Readhe- Ex. Adh. (Mrad) lease sion lease sion 1 ADH 14 21.7 1000 25.1 970 2 ADH 16 21.2 1040 27.9 1160 3 ADH 18 23.9 940 36.0 880 4 ADH 20 18.3 1040 20.8 1080

TABLE 1B Release and readhesion results for wet cast samples. Initial 90/90 (gm/2.54 cm) (gm/2.54 cm) Dose Re- Readhe- Re- Readhe- Ex. Adh. (Mrad) lease sion lease sion 1 ADH 14 42.0 820 80.9 1000 2 ADH 16 44.6 900 43.8 1120 3 ADH 18 46.6 1060 49.1 1210 4 ADH 20 44.8 1170 45.9 1370

Functional Silicone Materials. Examples 5 through 7 were prepared by electron beam curing a silanol terminated functional silicone fluid. Silanol terminated polydimethyl siloxane (DMS-542, 18,000 cSt, from Gelest) was coated with a flat, stiff blade to a coat weight of 1.3 to 2.3 gram/square meter on a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were electron beam cured in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV.

An acrylic foam tape (PT1100, available from 3M Company) was used to evaluate the release and readhesion to stainless steel after a three day dwell at room temperature (3d-RT) and a three day dwell at 70° C. (3d-HT). The adhesive was an acrylic/rubber blend. Release and readhesion was tested using a dry lamination process. First, the liner on the commercial PT1100 acrylic foam tape was removed and the release force recorded. Readhesion to stainless steel of this ‘as provided” material was also measured, for comparison purposes.

Next, the liner was removed from additional samples the PT1100 acrylic foam tape and the exposed adhesive was dry laminated to the e-beam cured silicone surfaces of the test samples. The samples were conditioned and the release force and readhesion force were measured. The results are summarized in Table 2.

TABLE 2 Release and readhesion results for e-beam cured, silanol functional silicones. 3 d-RT 3 d-HT (gm/2.54 cm) (gm/2.54 cm) Dose Re- Readhe- Re- Readhe- Ex. Adh. (Mrad) lease sion lease sion CE-1 PT1000 (*) 332 6760 472 6990 5 PT1000 12 306 3930 571 5630 6 PT1000 16 181 5940 415 7440 7 PT1000 19 106 9590 357 7920 (*) standard product liner, not an e-beam cured silicone.

Example 8 was prepared by electron beam curing an alkoxy terminated functional silicone fluid. Trimethyl siloxy terminated polydimethyl siloxane (DMS-T21, 100 cSt, from Gelest) was coated with a flat, stiff blade to a coat weight of 0.70 gram/square meter on a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were electron beam cured in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV and a dose of 16 MRad.

An acrylic foam tape (EX4011, available from 3M Company) was used to evaluate the release and readhesion to stainless steel after a seven day dwell at room temperature (7d-RT). The adhesive was an rubber/acrylic blend. Release and readhesion was tested using a dry lamination process. First, the liner on the commercial EX4011 acrylic foam tape was removed and the release force recorded. Readhesion to stainless steel of this ‘as provided” material was also measured, for comparison purposes.

Next, the liner was removed from additional samples the EX4011 acrylic foam tape and the exposed adhesive was dry laminated to the e-beam cured silicone surfaces of the test samples. The samples were conditioned and the release force and readhesion force were measured. The results are summarized in Table 3.

TABLE 3 Release and readhesion results for e-beam cured, functional silicones. 7 d-RT (gm/2.54 cm) Ex. Adh. Dose (Mrad) Release Readhesion CE-2 EX4011 (*) 304 4270 8 EX4011 16 244 1670 (*) standard product liner, not an e-beam cured silicone.

Although there was some cure of this trimethyl siloxy terminated polydimethyl siloxane, the low readhesion values indicate an under cured system.

The EX4011 acrylic foam tape adhesive was also dry laminated to a sample of silanol terminated polydimethyl siloxane (DMS-S42, 18,000 cSt, from Gelest) that was coated with a flat, stiff blade to a coat weight of 1.8 gram/square meter on a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were electron beam cured in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV and 16 Mrads. The 7d-RT release was 221 g/2.54 cm. The 7d-RT readhesion was 4560 gm/2.54 cm.

Other functional groups.

The following comparative example was prepared by attempting to electron beam curing a hydride functional silicone fluid. Hydride terminated polydimethyl siloxane (DMS-H25, 500 cSt, from Gelest) was coated with a flat, stiff blade to a coat a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were exposed to electron beam irradiation in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV and dose of 16 Mrad. The sample did not cure.

The following comparative example was prepared by attempting to electron beam curing a vinyl functional silicone fluid. Vinyl terminated polydimethyl siloxane (DMS-V42, 20,000 cSt, from Gelest) was coated with a flat, stiff blade to a coat a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were exposed to electron beam irradiation in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV and dose of 16 Mrad. The sample cured but did not anchor to the underlying polyethylene liner. The cured siloxane could be rubbed off the liner.

The following comparative example was prepared by attempting to electron beam curing a carboxyalkyl functional silicone fluid. Carboxyalkyl terminated polydimethyl siloxane (DMS-B31, 800-1200 cSt, from Gelest) was coated with a flat, stiff blade to a coat a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were exposed to electron beam irradiation in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV and dose of 16 Mrad. The sample did not cure.

Low kinematic viscosity sample. The following comparative example was prepared by attempting to electron beam curing a low viscosity, low molecular weight silanol functional silicone fluid. Silanol terminated polydimethyl siloxane (DMS-S12, 20 cSt, from Gelest) was coated with a flat, stiff blade to a coat a 115 micron (4.5 mil) thick polyethylene liner, which had been nitrogen corona treated at 0.71 Joule per square centimeter. The coated samples were exposed to electron beam irradiation in an inert atmosphere (less than 50 ppm oxygen) using an acceleration voltage of 250 keV and dose of 16 Mrad. The sample did not cure.

Blends of functional and non-functional.

For Examples 9 through 20 the following materials were used:

Trade Designation Description DC200 30,000 cSt and 100,000 cSt silicone fluids commercially available from Dow Corning RC902 a silicone acrylate polymer commercially available from Evonik/Goldschmidt DMS-V46 a vinyl terminated silicone polymer commercially available from Gelest F1-3546 a silicone hydride crosslinker commercially available from Dow Corning DMS-A32 an amine terminated silicone polymer commercially available from Gelest DBE-224 silicone-ethylene oxide copolymer commercially available from Gelest

Examples 9 to 20 include 75 wt % of the non-functional (i.e., DC200) material blended with 25 wt % of the functional material used for the individual examples (weight percents based on the total weight of the blend). The following examples were prepared by electron beam curing the silicone materials. Coating materials were prepared by dissolving the silicone in heptane to produce a 40 wt. % solids solution. This coating was applied with a flat stiff blade at 103 kPa (15 psi) pressure onto a polycoated kraft paper substrate (58# PCK from Jencoat). The samples were dried at room temperature. The resulting samples had a dry coat weight of 0.6 to 0.8 gram/square meter (0.14 to 0.20 grains per four inch by six inch sample).

The silicone materials were electron beam cured according to the following procedure. The samples were cured using an acceleration voltage of 120 keV at 10 Mrads of dose. The same test procedures for e-beam curing, release and readhesion were used for the following Examples as were used for Examples 1 to 8 above.

The electron beam dose, liner release and readhesion for the dry-laminated samples are summarized in Table 4. Similarly, the electron beam dose, liner release and readhesion for the wet-cast samples are summarized in Table 5. The release and readhesion were measured initially and after a five day dwell of the adhesive against the release coating at 32° C. (90° F.) and 90% relative humidity (90/90).

TABLE 4 Release and readhesion results for dry laminated samples, blended functional silicones [blends were at a 75:25 wt ratio] CT room aged 90/90 aged (gm/2.54 cm) (gm/2.54 cm) Re- Readhe- Re- Readhe- Ex. Adh. Composition lease sion lease sion 9 ADH 30K 40 856 46 1117 10 ADH 30K/RC902 39 865 45 1074 11 ADH 30K/DMS-V46 43 921 45 1103 12 ADH 30K/F1-3546 39 788 33 1089 13 ADH 30K/DMS-A32 52 774 110 1063 14 ADH 30K/DBE-224 467 451 1616 652 15 ADH 100K 47 831 44 1060 16 ADH 100K/RC902 40 797 39 1077 17 ADH 100K/DMS-V46 50 822 41 1168 18 ADH 100K/F1-3546 67 816 38 1006 19 ADH 100K/DMS-A32 62 842 123 1032 20 ADH 100K/DBE-224 486 675 1370 644

TABLE 5 Release and readhesion results for wet cast samples, blended functional silicones [blends were at a 75:25 wt ratio] CT room aged 90/90 aged (gm/2.54 cm) (gm/2.54 cm) Re- Readhe- Re- Readhe- Ex. Adh. Composition lease sion lease sion 9 ADH 30K 69 1211 64 1089 10 ADH 30K/RC902 72 1057 67 927 11 ADH 30K/DMS-V46 90 1225 61 950 12 ADH 30K/F1-3546 74 1060 55 1111 13 ADH 30K/DMS-A32 69 1143 117 1060 14 ADH 30K/DBE-224 132 581 1624 578

Examples 21 through 26 were prepared as described above for Example 9 through 20 and tested for release and readhesion using the same test procedures as those used for

Examples 1 to 8 above. For Examples 24 and 26, the composition includes 90 wt % of the non-functional (i.e., DC200) material blended with 10 wt % of the functional material based on the total weight of the blend composition. The functional material used in Examples 23 and 24 included a silicone acrylate blend including a ratio of 70 parts RC902 to 30 parts RC711, which is a solvent free silicone acrylate commercially available from Evonik. The electron beam dose, liner release and readhesion for the dry-laminated Examples 21 through 26 are summarized in Table 6.

TABLE 6 Release and readhesion results for dry laminated samples, blended functional silicones CT room aged 90/90 aged (gm/2.54 cm) (gm/2.54 cm) Dose Re- Readhe- Re- Readhe- Ex. Adh. Composition Mrad lease sion lease sion 21 ADH 30K 5 23 513 27 397 22 ADH 30K 10 43 992 42 1040 23 ADH 75:25 blend of 10 34 1063 35 1018 30K/(RC902/ RC711) 24 ADH 90:10 blend of 10 32 1154 40 1069 30K/(RC902/ RC711) 25 ADH 75:25 blend of 5 27 1055 39 1171 30K:DMS-V46 26 ADH 90:10 blend of 5 25 851 37 995 30K:DMS-V46

An exemplary release liner according to some embodiments of the present disclosure is illustrated in FIG. 1. Release liner 100 comprises substrate 120 with e-beam cured silicone release coating 130 associated with one major surface of substrate 120. In some embodiments, a second e-beam cured release layer may be associated with the second major surface of the substrate, opposite the first e-beam cured silicone release coating.

Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. 

1. A method of making a silicone release layer comprising: applying a composition comprising one or more polysiloxane materials on a substrate and electron beam curing the composition to crosslink the polysiloxane materials, wherein the polysiloxane materials is a blend of nonfunctional polysiloxanes and functional polysiloxanes.
 2. The method of claim 1, wherein the polysiloxane material consists essentially of one or more polysiloxane fluids having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes.
 3. The method of claim 1, wherein the polysiloxane materials comprise a poly dimethylsiloxane.
 4. The method of claim 1, wherein the functional polysiloxanes is selected from at least one of amine terminated polysiloxanes, alkoxy terminated polysiloxanes, silanol terminated polysiloxanes, vinyl terminated polysiloxanes, acrylate terminated polysiloxanes, and combinations thereof.
 5. The method of claim 1, wherein each functional polysiloxane is a polysiloxane fluid having a kinematic viscosity at 25° C. no greater than 100,000 centistokes.
 6. The method of claim 1, wherein the nonfunctional polysiloxane material comprises a polysiloxane fluid having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes.
 7. The method of claim 1, wherein the blend of nonfunctional polysiloxanes and functional polysiloxanes comprises at least 10 wt % of the functional polysiloxane material based on the total weight of the blend.
 8. The method of claim 1, wherein the blend of nonfunctional polysiloxanes and functional polysiloxanes comprises at least 25 wt % of the functional polysiloxane material based on the total weight of the blend
 9. The method of claim 1, wherein the composition is substantially free of catalysts and initiators.
 10. The method of claim 1, wherein the composition comprises no greater than 5 wt. % solvent.
 11. The method of claim 1, wherein the composition further comprises a cross-linking material.
 12. The method according to claim 10, wherein the cross-linking material is a methyl hydride cross-linking material.
 13. A release coated substrate made according to any one of the method of claim
 1. 14. A release coating comprising an electron beam cured composition, wherein the electron beam cured composition comprises a polysiloxane fluid having a kinematic viscosity at 25° C. no greater than 100,000 centistokes that has been crosslinked, wherein the polysiloxane materials is a blend of nonfunctional polysiloxanes and functional polysiloxanes.
 15. The release coating of claim 14, wherein the composition comprises a blend of nonfunctional polysiloxanes and functional polysiloxanes, each having a kinematic viscosity at 25° C. no greater than 100,000 centistokes, wherein the polysiloxane fluids have been crosslinked.
 16. The release coating according claim 14, wherein the functional polysiloxanes is selected from the group of amine terminated polysiloxanes, alkoxy terminated polysiloxanes, silanol terminated polysiloxanes, vinyl terminated polysiloxanes, acrylate terminated polysiloxanes, and combinations thereof.
 17. The release coating according to claim 14, wherein each functional polysiloxane is a polysiloxane fluid having a kinematic viscosity at 25° C. no greater than 100,000 centistokes.
 18. The release coating according to claim 14, wherein the nonfunctional polysiloxane material comprises a polysiloxane fluid having a kinematic viscosity at 25° C. of no greater than 100,000 centistokes.
 19. The release coating according to claim 14, wherein the blend of nonfunctional polysiloxanes and functional polysiloxanes comprises at least 10 wt % of the functional polysiloxane material based on the total weight of the blend.
 20. The release coating according to claim 14, wherein the blend of nonfunctional polysiloxanes and functional polysiloxanes comprises at least 25 wt % of the functional polysiloxane material based on the total weight of the blend.
 21. The release coating according to claim 14, wherein the composition is substantially free of catalysts and initiators.
 22. The release coating according to claim 14, wherein the composition comprises no greater than 5 wt % solvent.
 23. The release coating according to claim 14, wherein the composition further comprises a cross-linking material.
 24. The release coating according to claim 23, wherein the cross-linking material is a methyl hydride siloxane cross-linker. 